2630
K. Junge et al. / Tetrahedron: Asymmetry 15 (2004)2621–2631
132.2, 132.8, 132.8 (C-9,90,10,100); 132.3 (d, C-10); 133.6
(d, C-20); 133.7 (d, C-1); 134.3 (C-2); 139.2 (d, i-PC6H4);
159.1 (d, m-PC6H4). 31P NMR (162MHz, CDCl3):
d = 7.8. IR (KBr): 3049m, 3005 m, 2952 m, 2912 m,
2832 m, 1617 w, 1590 s, 1572 s, 1507 s, 1479 s, 1462
m, 1414 s, 1358 m, 1317 w, 1284 m, 1247 s, 1181 m,
1160 m, 1145 m, 1102 w, 1041 s, 992 m, 960 w, 934 m,
864 m, 814 s, 773 s, 748 s, 691 s, 658 m, 621 m, 565
m, 541 w, 520 m, 465 m, 417 m. MS (ESI): m/z
(%) = 418 ([M+], 100); 281 (6); 276 (30); 265 (31); 252
References
1. (a) Noyori, R. Asymmetric Catalysis in Organic Synthesis;
Wiley: New York, 1994; (b) Transition Metals for Organic
Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH: Wein-
heim, 1998; (c) Comprehensive Asymmetric Catalysis;
Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.;
Springer: Berlin, 1999.
2. Reviews: (a) MacCarthy, M.; Guiry, P. J. Tetrahedron
2001, 57, 3809–3843; (b) Zhang, X. Enantiomer 1999, 4,
541–555; (c) Gladiali, S.; Fabbri, D. Chem. Ber./Recl.
1997, 130, 543–554; (d) Lagasse, F.; Kagan, H. B. Chem.
Pharm. Bull. 2000, 48, 315–324.
(5); 108 (5). HRMS calcd for C29H23OP: 418.14865.
24
D
Found: 418.14343. ½a ¼ À15 (c 0.3, toluene).
3. Comprehensive Asymmetric Catalysis; Jacobsen, E. N.,
Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999;
Transition Metals for Organic Synthesis; Beller, M., Bolm,
C., Eds.; Wiley-VCH: Weinheim, 1998.
4.2.14.
4-(3,4-Dimethoxy)-phenyl-4,5-dihydro-3H-
dinaphtho[2,1-c;10,20-e]phosphepine 4n.
4. (a) Reetz, M. T.; Sell, T. Tetrahedron Lett. 2000, 41,
6333–6336; (b) Reetz, M. T.; Mehler, G. Angew. Chem.,
Int. Ed. 2000, 39, 3889–3891.
5'
8
4'
10'
3'
2'
6'
7'
OCH3
OCH3
CH2'
P
CH2
9'
9
1'
1
5. (a) Arnold, L. A.; Imobos, R.; Manoli, A.; de Vries, A. H.
M.; Naasz, R.; Feringa, B. Tetrahedron 2000, 56,
2865–2878; (b) van den Berg, M.; Minnaard, A. J.;
Schudde, E. P.; van Esch, J.; de Vries, A. H. M.; de Vries,
J. G.; Feringa, B. L. J. Am. Chem. Soc. 2000, 122,
11539–11540; (c) Minnaard, A. J.; vanden Berg, M.;
Schudde, E. P.; van Esch, J.; de Vries, A. H. M.; de Vries,
J. G.; Feringa, B. Chim. Oggi 2001, 19, 12–13.
6. (a) Claver, C.; Fernandez, E.; Gillon, A.; Heslop, K.;
Hyett, D. J.; Martorell, A.; Orpen, A. G.; Pringle, P. G.
Chem. Commun. 2000, 961–962; (b) Martorell, A.; Naasz,
R.; Feringa, B. L.; Pringle, P. G. Tetrahedron: Asymmetry
2001, 12, 2497–2499.
7. Recent review about monophosphines: (a) Komarov, I.
V.; Bo¨rner, A. Angew. Chem., Int. Ed. 2001, 40,
1197–1200; some successful previous examples: (b) Guil-
len, F.; Fiaud, J.-F. Tetrahedron Lett. 1999, 40,
2939–2942; (c) Knowles, W. S.; Sabacky, M. J.; Vineyard,
B. D. J. Chem. Soc., Chem. Commun. 1972, 10–11; (d)
Morrison, J. D.; Burnett, R. E.; Aguiar, A. M.; Morrow,
C. J.; Phillips, C. J. Am. Chem. Soc. 1971, 93, 1301–1303;
(e) Burk, M. J.; Feaster, J. E.; Harlow, R. L. Tetrahedron:
Asymmetry 1991, 2, 569–592; (f) Marinetti, A.; Mathey,
F.; Ricard, I. Organometallics 1993, 12, 1207–1212.
8. (a) Alexakis, A.; Benhhaim, C.; Rosset, S.; Human, M. J.
Am. Chem. Soc. 2002, 124, 5262–5263; (b) Boezio, A. A.;
Charette, A. B. J. Am. Chem. Soc. 2003, 125, 1692–1693;
(c) Piarulli, U.; Claverie, C.; Daudos, P.; Gennari, C.;
Minnaard, A. J.; Feringa, B. L. Org. Lett. 2003, 23,
4493–4496; (d) Jia, X.; Li, X.; Shi, Q.; Yao, X.; Chan, A.
S. J. Org. Chem. 2003, 68, 4539–4541; (e) Li, X.; Jia, X.;
Lu, G.; Au-Yeung, T. T.-L.; Lam, K.-H.; Lo, T. W. H.;
Chan, A. S. Tetrahedron: Asymmetry 2003, 14, 2687–2691;
(f) Au-Yeung, T. T.-L.; Chan, S.-S.; Chan, A. S. Adv.
Synth. Catal. 2003, 345, 537–555; (g) Reetz, M. T.; Oka,
H.; Goddard, R. Synthesis 2003, 12, 1809–1814; (h)
Jerphagon, T.; Renaud, J.-L.; Demonchaux, P.; Ferreira,
A.; Bruneau, C. Adv. Synth. Catal. 2004, 346, 33–36; (i)
van Zijl, A. W.; Arnold, L. A.; Minnaard, A. J.; Feringa,
B. L. Adv. Synth. Catal. 2004, 346, 413–420.
8'
7
6
2
3
10
5
4
1
Yield: 67%. H NMR (400MHz, CDCl3): d = 2.68 (dd,
1H, JH,H = 14.3Hz, JP,H = 4.5Hz, CH2(a)); 2.89 (dd,
1H, JP,H = 11.7Hz, CH2(b)); 2.96 (dq, 2H,
JH,H = 11.7Hz, CH02); 3.73 (s, 3H, CH3O); 3.90 (s, 3H,
CH3O); 6.70 (dd, 1H, o-PC6H3); 6.81 (d, 1H, m0-
PC6H3); 6.89 (m, 1H, o0-PC6H3); 7.03 (d, 1H, H-30);
7.17–7.32 (m, 4H, H-7,70,8,80); 7.40–7.47 (m, 2H, H-
6,60); 7.67 (dd, 1H, H-3); 7.80 (d, 1H, H-40); 7.89–7.97
(3d, 3H, H-4,5,50). 13C NMR (100.6MHz, CDCl3):
d = 31.1 (d, J = 15.5Hz, CH2); 32.7 (d, J = 22.0Hz,
CH2); 55.8, 55.8 (2CH3O); 110.9 (d, m0-PC6H3); 114.6
(d, o-PC6H3); 124.9, 125.0 (C-6, 60); 125.6 (d, o0-
PC6H3); 125.9, 125.9 (C-7,70); 126.62, 126.65 (C-8, 80);
127.3 (d, C-3); 127.4 (C-4); 128.0, 128.2, 128.4, 128.5
(C-30,4,5,50); 132.0, 132.3, 132.8, 132.8 (C-9, 90,10,100);
132.2 (d, C-10); 133.5 (d, C-1); 133.6 (C-20); 134.3 (C-
2); 148.5 (d, m-PC6H3); 149.1 (p-PC6H3). 31P NMR
(162MHz, CDCl3): d = 6.0. IR (KBr): 3056 m, 3002
m, 2955 m, 2835 m, 1592 s, 1506 s, 1463 s, 1441 s,
1397 m, 1359 w, 1329 m, 1254 s, 1231 s, 1176 s, 1144
m, 1124 s, 1027 s, 912 w, 867 w, 853 w, 814 m, 745 s,
683 w, 660 w, 622 w, 581 w, 544 w, 468 w, 419 m. MS
(ESI): m/z (%) = 448 ([M+], 100); 433 (7); 276 (17); 265
(19); 151 (15). HRMS calcd for C30H25O2P: 448.15921.
Found: 448.15980. ½a ¼ À33:5 (c 0.4, toluene).
24
D
Acknowledgements
The authorsthank M. Heyken, H. Baudicsh, Dr. W.
Baumann, S. Buchholz and Dr. C. Fischer (all IfOK)
for analytical and technical support. We also thank
Prof. Dr. S. Gladiali (University di Sassari, Italy) for
helpful discussions. Generous financial support of this
project from the state Mecklenburg-Western Pomerania
(Landesforschungsschwerpunkt), the Fonds der Chem-
ischen Industrie, and the Bundesministerium fur Bil-
¨
dung und Forschung (BMBF) is also gratefully
acknowledged.
9. Chen, W.; Xiao, J. Tetrahedron Lett. 2001, 42, 8737–8740.
10. Hua, Z.; Vassar, V. C.; Ojima, I. Org. Lett. 2003, 21,
3831–3834.
11. (a) Hu, A.-G.; Fu, Y.; Xie, J.-H.; Zhou, H.; Wang, L.-X.;
Zhou, Q.-L. Angew. Chem., Int. Ed. 2002, 41, 2348–2350;
(b) Fu, Y.; Xie, J.-H.; Hu, A.-G.; Zhou, H.; Wang, L.-X.;
Zhou, Q.-L. Chem. Commun. 2002, 480.
12. Ostermeier, M.; Prieß, J.; Helmchen, G. Angew. Chem.,
Int. Ed. 2002, 41, 612–617.